Steam strengthenable glass compositions with low phosphorous content

ABSTRACT

Glass-based articles that include a compressive stress layer extending from a surface of the glass-based article to a depth of compression are formed by exposing glass-based substrates to water vapor containing environments. The glass-based substrates include low amounts of phosphorous. The methods of forming the glass-based articles may include elevated pressures and/or multiple exposures to water vapor containing environments.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a continuation of International Application No. PCT/US20/32424 filed May 12, 2020, which claims the priority benefit of U.S. Application No. 62/848,791 filed May 16, 2019, and this Application is a continuation-in-part of International Application No. PCT/US20/32432 filed May 12, 2020, which claims the priority benefit of U.S. Application No. 62/848,805 filed May 16, 2019, each of which is incorporated by reference herein in its entirety.

BACKGROUND Field

This disclosure relates to glass-based articles strengthened by steam treatment, alkali-free glass compositions utilized to form the glass-based articles, and methods of steam treatment to strengthen the glass-based articles.

Technical Background

Portable electronic devices, such as, smartphones, tablets, and wearable devices (such as, for example, watches and fitness trackers) continue to get smaller and more complex. As such, materials that are conventionally used on at least one external surface of such portable electronic devices also continue to get more complex. For instance, as portable electronic devices get smaller and thinner to meet consumer demand, the display covers and housings used in these portable electronic devices also get smaller and thinner, resulting in higher performance requirements for the materials used to form these components.

Accordingly, a need exists for materials that exhibit higher performance, such as resistance to damage, along with lower cost and ease of manufacture for use in portable electronic devices.

SUMMARY

In aspect (1), a glass-based article is provided. The glass-based article comprises: a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer, wherein a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer; a compressive stress layer extending from the surface of the glass-based article to a depth of compression, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 10 MPa; and a composition at the center of the glass-based article comprising:

-   -   greater than or equal to 55 mol % to less than or equal to 70         mol % SiO₂,     -   greater than or equal to 5 mol % to less than or equal to 13 mol         % Al₂O₃,     -   greater than or equal to 0.1 mol % to less than or equal to 3         mol % P₂O₅,     -   greater than or equal to 14 mol % to less than or equal to 23         mol % K₂O, and     -   greater than or equal to 1 mol % to less than or equal to 4 mol         % ZnO.

In aspect (2), the glass-based article of aspect (1) is provided, wherein the composition at the center of the glass-based article further comprises greater than or equal to 0 mol % to less than or equal to 5 mol % B₂O₃.

In aspect (3), the glass-based article of aspect (1) or (2) is provided, wherein the composition at the center of the glass-based article further comprises greater than or equal to 0 mol % to less than or equal to 1 mol % Na₂O.

In aspect (4), the glass-based article of any of aspects (1) to (3) is provided, wherein the composition at the center of the glass-based article is substantially free of Na₂O.

In aspect (5), the glass-based article of any of aspects (1) to (4) is provided, wherein the composition at the center of the glass-based article further comprises greater than or equal to 0 mol % to less than or equal to 7 mol % MgO.

In aspect (6), the glass-based article of any of aspects (1) to (5) is provided, wherein the composition at the center of the glass-based article further comprises greater than or equal to 0 mol % to less than or equal to 0.5 mol % SnO₂.

In aspect (7), the glass-based article of any of aspects (1) to (6) is provided, comprising a thickness of less than or equal to 2 mm.

In aspect (8), the glass-based article of any of aspects (1) to (7) is provided, comprising a compressive stress of greater than or equal to 100 MPa.

In aspect (9), the glass-based article of any of aspects (1) to (8) is provided, comprising a compressive stress of greater than or equal to 300 MPa.

In aspect (10), the glass-based article of any of aspects (1) to (9) is provided, wherein the depth of compression is greater than or equal to 6 μm.

In aspect (11), the glass-based article of any of aspects (1) to (10) is provided, wherein the depth of compression is greater than or equal to 10 μm.

In aspect (12), the glass-based article of any of aspects (1) to (11) is provided, wherein the glass-based article has a substantially haze-free appearance.

In aspect (13), a consumer electronic product is provided. The consumer electronic product comprises: a housing comprising a front surface, a back surface and side surfaces; electrical components at least partially within the housing, the electrical components comprising at least a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display. At least a portion of at least one of the housing and the cover substrate comprises the glass-based article of any of aspects (1) to (12).

In aspect (14), a glass is provided. The glass comprises:

-   -   greater than or equal to 55 mol % to less than or equal to 70         mol % SiO₂,     -   greater than or equal to 5 mol % to less than or equal to 13 mol         % Al₂O₃,     -   greater than or equal to 0.1 mol % to less than or equal to 3         mol % P₂O₅,     -   greater than or equal to 14 mol % to less than or equal to 23         mol % K₂O, and     -   greater than or equal to 1 mol % to less than or equal to 4 mol         % ZnO.

In aspect (15), the glass of aspect (14) is provided, further comprising greater than or equal to 0 mol % to less than or equal to 5 mol % B₂O₃.

In aspect (16), the glass of aspect (14) or (15) is provided, further comprising greater than or equal to 0 mol % to less than or equal to 1 mol % Na₂O.

In aspect (17), the glass of any of aspects (14) to (16) is provided, wherein the glass is substantially free of Na₂O.

In aspect (18), the glass of any of aspects (14) to (17) is provided, further comprising greater than or equal to 0 mol % to less than or equal to 7 mol % MgO.

In aspect (19), the glass of any of aspects (14) to (18) is provided, further comprising greater than or equal to 0 mol % to less than or equal to 0.5 mol % SnO₂.

In aspect (20), the glass of any of aspects (14) to (19) is provided, further comprising a Young's modulus of greater than or equal to 59 MPa.

In aspect (21), a method is provided. The method comprises: exposing a glass-based substrate to a steam environment with a pressure greater than or equal to 0.1 MPa, and a temperature of greater than or equal to 150° C. to form a glass-based article with compressive stress layer extending from the surface of the glass-based article to a depth of compression and a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer. The compressive stress layer comprises a compressive stress of greater than or equal to 10 MPa. A hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer. The glass-based substrate comprises:

-   -   greater than or equal to 55 mol % to less than or equal to 70         mol % SiO₂,     -   greater than or equal to 5 mol % to less than or equal to 13 mol         % Al₂O₃,     -   greater than or equal to 0.1 mol % to less than or equal to 3         mol % P₂O₅,     -   greater than or equal to 14 mol % to less than or equal to 23         mol % K₂O, and     -   greater than or equal to 1 mol % to less than or equal to 4 mol         % ZnO.

In aspect (22), the method of aspect (21) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 5 mol % B₂O₃.

In aspect (23), the method of aspect (21) or (22) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 1 mol % Na₂O.

In aspect (24), the method of any of aspects (21) to (23) is provided, wherein the glass-based substrate is substantially free of Na₂O.

In aspect (25), the method of any of aspects (21) to (24) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 7 mol % MgO.

In aspect (26), the method of any of aspects (21) to (25) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 0.5 mol % SnO₂.

In aspect (27), the method of any of aspects (21) to (26) is provided, wherein the glass-based substrate comprises a Young's modulus of greater than or equal to 59 MPa.

In aspect (28), the method of any of aspects (21) to (27) is provided, further comprising exposing the glass-based article to a second steam environment with a second pressure and a second temperature, wherein the second steam environment is a saturated steam environment.

In aspect (29), the method of any of aspects (21) to (28) is provided, wherein the glass-based article comprises a thickness of less than or equal to 2 mm.

In aspect (30), the method of any of aspects (21) to (29) is provided, wherein the glass-based article comprises a compressive stress of greater than or equal to 100 MPa.

In aspect (31), the method of any of aspects (21) to (30) is provided, wherein the glass-based article comprises a compressive stress of greater than or equal to 300 MPa.

In aspect (32), the method of any of aspects (21) to (31) is provided, wherein the depth of compression is greater than or equal to 6 μm.

In aspect (33), the method of any of aspects (21) to (32) is provided, wherein the depth of compression is greater than or equal to 10 μm.

In aspect (34), the method of any of aspects (21) to (33) is provided, wherein the glass-based article has a substantially haze-free appearance.

In aspect (35), the method of any of aspects (21) to (34) is provided, wherein the glass-based article is not subjected to an ion-exchange treatment with an alkali ion source.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representation of a cross-section of a glass-based article according to an embodiment.

FIG. 2A is a plan view of an exemplary electronic device incorporating any of the glass-based articles disclosed herein.

FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A.

FIG. 3 is a plot of the saturation condition for water as a function or pressure and temperature.

DETAILED DESCRIPTION

In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range as well as any sub-ranges therebetween. As used herein, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more,” unless otherwise specified. It also is understood that the various features disclosed in the specification and the drawings can be used in any and all combinations.

As used herein, the term “glass-based” is used in its broadest sense to include any objects made wholly or partly of glass, including glass ceramics (which include a crystalline phase and a residual amorphous glass phase). Unless otherwise specified, all compositions of the glasses described herein are expressed in terms of mole percent (mol %), and the constituents are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in terms of degrees Celsius (° C.).

It is noted that the terms “substantially” and “about” may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. For example, a glass that is “substantially free of K₂O” is one in which K₂O is not actively added or batched into the glass but may be present in very small amounts as a contaminant, such as in amounts of less than about 0.01 mol %. As utilized herein, when the term “about” is used to modify a value, the exact value is also disclosed. For example, the term “greater than about 10 mol %” also discloses “greater than or equal to 10 mol %.”

Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying examples and drawings.

The glass-based articles disclosed herein are formed by steam treating a glass-based substrate to produce a compressive stress layer extending from surface of the article to a depth of compression (DOC). The term “steam” is utilized interchangeably herein with the term “water vapor.” The compressive stress layer includes a stress that decreases from a maximum stress to the depth of compression. In some embodiments, the maximum compressive stress may be located at the surface of the glass-based article. As used herein, depth of compression (DOC) means the depth at which the stress in the glass-based article changes from compressive to tensile. Thus, the glass-based article also contains a tensile stress region having a maximum central tension (CT), such that the forces within the glass-based article are balanced.

The glass-based articles further include a hydrogen-containing layer extending from a surface of the article to a depth of layer. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration of the glass-based article to the depth of layer. In some embodiments, the maximum hydrogen concentration may be located at the surface of the glass-based article.

The glass-based articles may be formed by exposing glass-based substrates to environments containing water vapor, thereby allowing hydrogen species to penetrate the glass-based substrates and form the glass-based articles having a hydrogen-containing layer and/or a compressive stress layer. As utilized herein, hydrogen species includes molecular water, hydroxyl, hydrogen ions, and hydronium. The composition of the glass-based substrates may be selected to promote the interdiffusion of hydrogen species into the glass. As utilized herein, the term “glass-based substrate” refers to the precursor prior to exposure to a water vapor containing environment for the formation of a glass-based article that includes hydrogen-containing layers and/or compressive stress layers. Similarly, the term “glass-based article” refers to the post exposure article that includes a hydrogen-containing layer and/or a compressive stress layer.

The glass-based articles disclosed herein may exhibit a compressive stress layer without undergoing conventional ion exchange, thermal tempering, or lamination treatments. Ion exchange processes produce significant waste in the form of expended molten salt baths that require costly disposal, and also are applicable to only some glass compositions. Thermal tempering requires thick glass specimens as a practical matter, as thermal tempering of thin sheets utilizes small air gap quenching processes which results in sheet scratching damage that reduces performance and yield. Additionally, it is difficult to achieve uniform compressive stress across surface and edge regions when thermal tempering thin glass sheets. Laminate processes result in exposed tensile stress regions when large sheets are cut to usable sizes, which is undesirable.

The water vapor treatment utilized to form the glass-based articles allows for reduced waste and lower cost when compared to ion exchange treatments as molten salts are not utilized, and alkali-free glass-based substrates may be employed. The water vapor treatment is also capable of strengthening thin (<2 mm) low-cost glass that would not be suitable for thermal tempering at such thicknesses. Additionally, the water vapor treatment may be performed at the part level, avoiding the undesirable exposed tensile stress regions associated with laminate processes. In sum, the glass-based articles disclosed herein may be produced with a low thickness and at a low cost while exhibiting a high compressive stress and deep depth of compression.

A representative cross-section of a glass-based article 100 according to some embodiments is depicted in FIG. 1. The glass-based article 100 has a thickness t that extends between a first surface 110 and a second surface 112. A first compressive stress layer 120 extends from the first surface 110 to a first depth of compression, where the first depth of compression has a depth d₁ measured from the first surface 110 into the glass-based article 100. A second compressive stress layer 122 extends from the second surface 112 to a second depth of compression, where the second depth of compression has a depth d₂ measured from the second surface 112 into the glass-based article 100. A tensile stress region 130 is present between the first depth of compression and the second depth of compression. In embodiments, the first depth of compression d₁ may be substantially equivalent or equivalent to the second depth of compression d₂.

In some embodiments, the compressive stress layer of the glass-based article may include a compressive stress of at greater than or equal to 10 MPa, such as greater than or equal to 20 MPa, greater than or equal to 30 MPa, greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, greater than or equal to 90 MPa, greater than or equal to 100 MPa, greater than or equal to 110 MPa, greater than or equal to 120 MPa, greater than or equal to 130 MPa, greater than or equal to 140 MPa, greater than or equal to 145 MPa, greater than or equal to 150 MPa, greater than or equal to 160 MPa, greater than or equal to 170 MPa, greater than or equal to 180 MPa, greater than or equal to 190 MPa, greater than or equal to 200 MPa, greater than or equal to 210 MPa, greater than or equal to 220 MPa, greater than or equal to 230 MPa, greater than or equal to 240 MPa, greater than or equal to 250 MPa, greater than or equal to 260 MPa, greater than or equal to 270 MPa, greater than or equal to 280 MPa, greater than or equal to 290 MPa, greater than or equal to 300 MPa, greater than or equal to 310 MPa, greater than or equal to 320 MPa, greater than or equal to 330 MPa, greater than or equal to 340 MPa, greater than or equal to 350 MPa, greater than or equal to 360 MPa, greater than or equal to 370 MPa, greater than or equal to 380 MPa, greater than or equal to 390 MPa, greater than or equal to 400 MPa, greater than or equal to 410 MPa, greater than or equal to 420 MPa, greater than or equal to 430 MPa, greater than or equal to 440 MPa, greater than or equal to 450 MPa, greater than or equal to 460 MPa, greater than or equal to 470 MPa, greater than or equal to 480 MPa, greater than or equal to 490 MPa, greater than or equal to 500 MPa, greater than or equal to 510 MPa, greater than or equal to 520 MPa, greater than or equal to 530 MPa, greater than or equal to 540 MPa, or more. In some embodiments, the compressive stress layer may include a compressive stress of from greater than or equal to 10 MPa to less than or equal to 550 MPa, such as from greater than or equal to 20 MPa to less than or equal to 540 MPa, from greater than or equal to 30 MPa to less than or equal to 530 MPa, from greater than or equal to 40 MPa to less than or equal to 520 MPa, from greater than or equal to 50 MPa to less than or equal to 510 MPa, from greater than or equal to 60 MPa to less than or equal to 500 MPa, from greater than or equal to 70 MPa to less than or equal to 490 MPa, from greater than or equal to 80 MPa to less than or equal to 480 MPa, from greater than or equal to 90 MPa to less than or equal to 470 MPa, from greater than or equal to 100 MPa to less than or equal to 460 MPa, from greater than or equal to 110 MPa to less than or equal to 450 MPa, from greater than or equal to 120 MPa to less than or equal to 440 MPa, from greater than or equal to 130 MPa to less than or equal to 430 MPa, from greater than or equal to 140 MPa to less than or equal to 420 MPa, from greater than or equal to 150 MPa to less than or equal to 410 MPa, from greater than or equal to 160 MPa to less than or equal to 400 MPa, from greater than or equal to 170 MPa to less than or equal to 390 MPa, from greater than or equal to 180 MPa to less than or equal to 380 MPa, from greater than or equal to 190 MPa to less than or equal to 370 MPa, from greater than or equal to 200 MPa to less than or equal to 360 MPa, from greater than or equal to 210 MPa to less than or equal to 350 MPa, from greater than or equal to 220 MPa to less than or equal to 340 MPa, from greater than or equal to 230 MPa to less than or equal to 330 MPa, from greater than or equal to 240 MPa to less than or equal to 320 MPa, from greater than or equal to 250 MPa to less than or equal to 310 MPa, from greater than or equal to 260 MPa to less than or equal to 300 MPa, from greater than or equal to 270 MPa to less than or equal to 290 MPa, 280 MPa, or any sub-ranges formed from any of these endpoints.

In some embodiments, the DOC of the compressive stress layer may be greater than or equal to 4 μm, such as greater than or equal to 5 μm, greater than or equal to 6 μm, greater than or equal to 7 μm, greater than or equal to 10 μm, greater than or equal to 15 μm, greater than or equal to 20 μm, greater than or equal to 25 μm, greater than or equal to 30 μm, greater than or equal to 35 μm, greater than or equal to 40 μm, greater than or equal to 45 μm, greater than or equal to 50 μm, greater than or equal to 55 μm, greater than or equal to 60 μm, greater than or equal to 65 μm, greater than or equal to 70 μm, greater than or equal to 75 μm, greater than or equal to 80 μm, greater than or equal to 85 μm, greater than or equal to 90 μm, greater than or equal to 95 μm, greater than or equal to 100 μm, greater than or equal to 105 μm, greater than or equal to 110 μm, or more. In some embodiments, the DOC of the compressive stress layer may be from greater than or equal to 4 μm to less than or equal to 115 μm, such as from greater than or equal to 5 μm to less than or equal to 110 μm, from greater than or equal to 10 μm to less than or equal to 100 μm, from greater than or equal to 15 μm to less than or equal to 95 μm, from greater than or equal to 20 μm to less than or equal to 90 μm, from greater than or equal to 25 μm to less than or equal to 85 μm, from greater than or equal to 30 μm to less than or equal to 80 μm, from greater than or equal to 35 μm to less than or equal to 75 μm, from greater than or equal to 40 μm to less than or equal to 70 μm, from greater than or equal to 45 μm to less than or equal to 65 μm, from greater than or equal to 50 μm to less than or equal to 60 μm, 55 μm, or any sub-ranges that may be formed from any of these endpoints.

In some embodiments, the glass-based articles may have a DOC greater than or equal to 0.05 t, wherein t is the thickness of the glass-based article, such as greater than or equal to 0.06 t, greater than or equal to 0.07 t, greater than or equal to 0.08 t, greater than or equal to 0.09 t, greater than or equal to 0.10 t, greater than or equal to 0.11 t, greater than or equal to 0.12 t, greater than or equal to 0.13 t, greater than or equal to 0.14 t, greater than or equal to 0.15 t, greater than or equal to 0.16 t, greater than or equal to 0.17 t, greater than or equal to 0.18 t, greater than or equal to 0.19 t, or more. In some embodiments, the glass-based articles may have a DOC from greater than or equal to 0.05 t to less than or equal to 0.20 t, such as from greater than or equal to 0.06 t to less than or equal to 0.19 t, from greater than or equal to 0.07 t to less than or equal to 0.18 t, from greater than or equal to 0.08 t to less than or equal to 0.17 t, from greater than or equal to 0.09 t to less than or equal to 0.16 t, from greater than or equal to 0.10 t to less than or equal to 0.15 t, from greater than or equal to 0.11 t to less than or equal to 0.14 t, from greater than or equal to 0.12 t to less than or equal to 0.13 t, or any sub-ranges formed from any of these endpoints.

Compressive stress (including surface CS) is measured by surface stress meter using commercially available instruments such as the FSM-6000 (FSM), manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC in turn is measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety. DOC is measured by FSM. The maximum central tension (CT) values are measured using a scattered light polariscope (SCALP) technique known in the art.

The hydrogen-containing layer of the glass-based articles may have a depth of layer (DOL) greater than 5 μm. In some embodiments, the depth of layer may be greater than or equal to 10 μm, such as greater than or equal to 15 μm, greater than or equal to 20 μm, greater than or equal to 25 μm, greater than or equal to 30 μm, greater than or equal to 35 μm, greater than or equal to 40 μm, greater than or equal to 45 μm, greater than or equal to 50 μm, greater than or equal to 55 μm, greater than or equal to 60 μm, greater than or equal to 65 μm, greater than or equal to 70 μm, greater than or equal to 75 μm, greater than or equal to 80 μm, greater than or equal to 85 μm, greater than or equal to 90 μm, greater than or equal to 95 μm, or more. In some embodiments, the depth of layer may be from greater than 5 μm to less than or equal to 100 μm, such as from greater than or equal to 10 μm to less than or equal to 95 μm, from greater than or equal to 15 μm to less than or equal to 90 μm, from greater than or equal to 20 μm to less than or equal to 85 μm, from greater than or equal to 25 μm to less than or equal to 80 μm, from greater than or equal to 30 μm to less than or equal to 75 μm, from greater than or equal to 35 μm to less than or equal to 70 μm, from greater than or equal to 40 μm to less than or equal to 65 μm, from greater than or equal to 45 μm to less than or equal to 60 μm, from greater than or equal to 50 μm to less than or equal to 55 μm, or any sub-ranges formed by any of these endpoints. In general, the depth of layer exhibited by the glass-based articles is greater than the depth of layer that may be produced by exposure to the ambient environment.

The hydrogen-containing layer of the glass-based articles may have a depth of layer (DOL) greater than 0.005 t, wherein t is the thickness of the glass-based article. In some embodiments, the depth of layer may be greater than or equal to 0.010 t, such as greater than or equal to 0.015 t, greater than or equal to 0.020 t, greater than or equal to 0.025 t, greater than or equal to 0.030 t, greater than or equal to 0.035 t, greater than or equal to 0.040 t, greater than or equal to 0.045 t, greater than or equal to 0.050 t, greater than or equal to 0.055 t, greater than or equal to 0.060 t, greater than or equal to 0.065 t, greater than or equal to 0.070 t, greater than or equal to 0.075 t, greater than or equal to 0.080 t, greater than or equal to 0.085 t, greater than or equal to 0.090 t, greater than or equal to 0.095 t, greater than or equal to 0.10 t, greater than or equal to 0.15 t, greater than or equal to 0.20 t, or more. In some embodiments, the DOL may be from greater than 0.005 t to less than or equal to 0.205 t, such as from greater than or equal to 0.010 t to less than or equal to 0.200 t, from greater than or equal to 0.015 t to less than or equal to 0.195 t, from greater than or equal to 0.020 t to less than or equal to 0.190 t, from greater than or equal to 0.025 t to less than or equal to 0.185 t, from greater than or equal to 0.030 t to less than or equal to 0.180 t, from greater than or equal to 0.035 t to less than or equal to 0.175 t, from greater than or equal to 0.040 t to less than or equal to 0.170 t, from greater than or equal to 0.045 t to less than or equal to 0.165 t, from greater than or equal to 0.050 t to less than or equal to 0.160 t, from greater than or equal to 0.055 t to less than or equal to 0.155 t, from greater than or equal to 0.060 t to less than or equal to 0.150 t, from greater than or equal to 0.065 t to less than or equal to 0.145 t, from greater than or equal to 0.070 t to less than or equal to 0.140 t, from greater than or equal to 0.075 t to less than or equal to 0.135 t, from greater than or equal to 0.080 t to less than or equal to 0.130 t, from greater than or equal to 0.085 t to less than or equal to 0.125 t, from greater than or equal to 0.090 t to less than or equal to 0.120 t, from greater than or equal to 0.095 t to less than or equal to 0.115 t, from greater than or equal to 0.100 t to less than or equal to 0.110 t, or any sub-ranges formed by any of these endpoints.

The depth of layer and hydrogen concentration may be measured by a secondary ion mass spectrometry (SIMS) technique that is known in the art. The SIMS technique is capable of measuring the hydrogen concentration at a given depth but is not capable of distinguishing the hydrogen species present in the glass-based article. For this reason, all hydrogen species contribute to the SIMS measured hydrogen concentration. As utilized herein, the depth of layer (DOL) refers to the first depth below the surface of the glass-based article where the hydrogen concentration is equal to the hydrogen concentration at the center of the glass-based article. This definition accounts for the hydrogen concentration of the glass-based substrate prior to treatment, such that the depth of layer refers to the depth of the hydrogen added by the treatment process. As a practical matter, the hydrogen concentration at the center of the glass-based article may be approximated by the hydrogen concentration at the depth from the surface of the glass-based article where the hydrogen concentration becomes substantially constant, as the hydrogen concentration is not expected to change between such a depth and the center of the glass-based article. This approximation allows for the determination of the DOL without measuring the hydrogen concentration throughout the entire depth of the glass-based article. In some embodiments, the presence of a hydrogen-containing layer may be inferred by the formation of a compressive stress layer as a result of water vapor treatment.

Without wishing to be bound by any particular theory, the hydrogen-containing layer of the glass-based articles may be the result of an interdiffusion of hydrogen species for ions contained in the compositions of the glass-based substrate. Hydrogen-containing species, such as H₃O⁺, H₂O, and/or H⁺, may diffuse into the glass-based substrate to form the glass-based article. Water could penetrate the glass-based substrates by forming silanol groups, breaking the network structure and causing a volume expansion of the glass. Such a volume expansion may generate a compressive stress layer in the glass-based articles. The compressive stress and depth of compression of the compressive stress layer may depend on the composition of the glass-based substrate utilized to form the glass-based article, and the water vapor treatment conditions, such as temperature, pressure, water content, and duration. The stress profile of the glass-based articles produced by the water vapor treatment may be similar to stress profiles produced by potassium for sodium ion exchange strengthening processes.

The glass-based articles that have compressive stress layers also exhibit weight gain when compared to the glass-based substrates prior to the water vapor treatment process. The weight gain of the glass-based articles indicates the formation of a hydrogen-containing layer as a result of the water vapor treatment. In some cases, the weight gain may be calculated as a percentage change from the weight of the glass-based substrate prior to the water vapor treatment.

The glass-based articles disclosed herein may be incorporated into another article such as an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof. An exemplary article incorporating any of the glass-based articles disclosed herein is shown in FIGS. 2A and 2B. Specifically, FIGS. 2A and 2B show a consumer electronic device 200 including a housing 202 having front 204, back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display. In some embodiments, at least a portion of at least one of the cover substrate 212 and the housing 202 may include any of the glass-based articles disclosed herein.

The glass-based articles may be formed from glass-based substrates having any appropriate composition. The composition of the glass-based substrate may be specifically selected to promote the diffusion of hydrogen-containing species, such that a glass-based article including a hydrogen-containing layer and a compressive stress layer may be formed efficiently. The glass-based substrates may have a composition that includes SiO₂, Al₂O₃, K₂O, ZnO, and P₂O₅. The content of P₂O₅ in the glass-based substrates may be low. The reduced P₂O₅ content may allow for higher compressive stresses for a given water vapor treatment condition than glass-based substrates with a higher P₂O₅ content. The low P₂O₅ glass-based substrates may also improve the durability of the glass-based substrates and the articles produced therefrom.

In some embodiments, the hydrogen species does not diffuse to the center of the glass-based article. Stated differently, the center of the glass-based article is the area least affected by the water vapor treatment. For this reason, the center of the glass-based article may have a composition that is substantially the same, or the same, as the composition of the glass-based substrate prior to treatment in the water containing environment.

The glass-based substrate may include any appropriate amount of SiO₂. SiO₂ is the largest constituent and, as such, SiO₂ is the primary constituent of the glass network formed from the glass composition. If the concentration of SiO₂ in the glass composition is too high, the formability of the glass composition may be diminished as higher concentrations of SiO₂ increase the difficulty of melting the glass, which, in turn, adversely impacts the formability of the glass. In some embodiments, the glass-based substrate may include SiO₂ in an amount from greater than or equal to 55 mol % to less than or equal to 70 mol %, such as from greater than or equal to 56 mol % to less than or equal to 69 mol %, from greater than or equal to 57 mol % to less than or equal to 68 mol %, from greater than or equal to 58 mol % to less than or equal to 67 mol %, from greater than or equal to 59 mol % to less than or equal to 66 mol %, from greater than or equal to 60 mol % to less than or equal to 65 mol %, from greater than or equal to 61 mol % to less than or equal to 64 mol %, from greater than or equal to 62 mol % to less than or equal to 63 mol %, 62 mol %, or any sub-ranges formed by any of these endpoints.

The glass-based substrate may include any appropriate amount of Al₂O₃. Al₂O₃ may serve as a glass network former, similar to SiO₂. Al₂O₃ may increase the viscosity of the glass composition due to its tetrahedral coordination in a glass melt formed from a glass composition, decreasing the formability of the glass composition when the amount of Al₂O₃ is too high. However, when the concentration of Al₂O₃ is balanced against the concentration of SiO₂ and the concentration of alkali oxides in the glass composition, Al₂O₃ can reduce the liquidus temperature of the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as the fusion forming process. The inclusion of Al₂O₃ in the glass-based substrate prevents phase separation and reduces the number of non-bridging oxygens (NBOs) in the glass. Additionally, Al₂O₃ can improve the effectiveness of ion exchange. In some embodiments, the glass-based substrate may include Al₂O₃ in an amount of from greater than or equal to 5 mol % to less than or equal to 13 mol %, such as from greater than or equal to 6 mol % to less than or equal to 12 mol %, from greater than or equal to 7 mol % to less than or equal to 11 mol %, from greater than or equal to 8 mol % to less than or equal to 10 mol %, 9 mol %, or any sub-ranges formed by any of these endpoints.

The glass-based substrate may include any amount of P₂O₅ sufficient to produce the desired hydrogen diffusivity in combination with the desired compressive stress capability. The inclusion of phosphorous in the glass-based substrate promotes faster interdiffusion. Thus, the phosphorous containing glass-based substrates allow the efficient formation of glass-based articles including a hydrogen-containing layer. The inclusion of P₂O₅ also allows for the production of a glass-based article with a deep depth of compression (e.g., greater than about 10 μm) in a relatively short treatment time. The low P₂O₅ content also increases the durability of the glass-based substrate, such that higher temperature and/or higher-pressure water vapor treatment environments may be employed without undesirable surface degradation. The avoidance of surface degradation is evidenced by a lack of a hazy appearance of the glass-based articles produced from the glass-based substrates. As discussed above, low P₂O₅ content of the glass-based substrates also increases the compressive stress capability of the glass-based substrates. If the P₂O₅ content in the glass-based substrates is too low, the diffusivity may be reduced. This reduction in diffusivity may be offset by the ability to employ higher temperature and pressure conditions due to the improved durability of the glass-based substrates. Additionally, if the P₂O₅ content in the glass-based substrates is too low the liquidus temperature may be increased, which may limit the manufacturing techniques that may be utilized to produce the glass-based substrates.

In some embodiments, the glass-based substrate may include P₂O₅ in an amount of from greater than or equal to 0.1 mol % to less than or equal to 3 mol %, such as from greater than or equal to 0.2 mol % to less than or equal to 3.9 mol %, from greater than or equal to 0.3 mol % to less than or equal to 3.8 mol %, from greater than or equal to 0.4 mol % to less than or equal to 3.7 mol %, from greater than or equal to 0.5 mol % to less than or equal to 3.6 mol %, from greater than or equal to 0.6 mol % to less than or equal to 3.5 mol %, from greater than or equal to 0.7 mol % to less than or equal to 3.4 mol %, from greater than or equal to 0.8 mol % to less than or equal to 3.3 mol %, from greater than or equal to 0.9 mol % to less than or equal to 3.2 mol %, from greater than or equal to 1.0 mol % to less than or equal to 3.1 mol %, from greater than or equal to 1.1 mol % to less than or equal to 3.0 mol %, from greater than or equal to 1.2 mol % to less than or equal to 2.9 mol %, from greater than or equal to 1.3 mol % to less than or equal to 2.8 mol %, from greater than or equal to 1.4 mol % to less than or equal to 2.7 mol %, from greater than or equal to 1.5 mol % to less than or equal to 2.6 mol %, from greater than or equal to 1.6 mol % to less than or equal to 2.5 mol %, from greater than or equal to 1.7 mol % to less than or equal to 2.4 mol %, from greater than or equal to 1.8 mol % to less than or equal to 2.3 mol %, from greater than or equal to 1.9 mol % to less than or equal to 2.2 mol %, from greater than or equal to 2.0 mol % to less than or equal to 2.1 mol %, or any sub-ranges formed by any of these endpoints.

The glass-based substrates may include any appropriate amount of K₂O. The inclusion of K₂O allows, at least in part, the efficient exchange of hydrogen species into the glass substrate upon exposure to a water vapor containing environment. The inclusion of K₂O also contributes to a reduction in the bulk Young's modulus of the glass-based substrates. In embodiments, the glass-based substrate may include K₂O in an amount of from greater than or equal to 14 mol % to less than or equal to 23 mol %, such as from greater than or equal to 15 mol % to less than or equal to 22 mol %, from greater than or equal to 16 mol % to less than or equal to 21 mol %, from greater than or equal to 17 mol % to less than or equal to 20 mol %, from greater than or equal to 18 mol % to less than or equal to 19 mol %, or any sub-ranges formed from any of these endpoints. In embodiments, the glass-based substrates may be substantially free or free of alkali metal oxides other than K₂O, such as Li₂O, Na₂O, Cs₂O, and Rb₂O.

The glass-based substrates may include any appropriate amount of ZnO. In some embodiments, the glass-based substrates may include ZnO in an amount from greater than or equal to 1 mol % to less than or equal to 4 mol %, such as from greater than or equal to 2 mol % to less than or equal to 3 mol %, or any and all sub-ranges formed from these endpoints.

The glass-based substrate may additionally include B₂O₃. The inclusion of B₂O₃ in the glass-based substrates may increase the damage resistance of the glass-based substrates, and thereby increase the damage resistance of the glass-based articles formed therefrom. In some embodiments, the glass-based substrates may include B₂O₃ in an amount from greater than or equal to 0 mol % to less than or equal to 5 mol %, such as from greater than or equal to 1 mol % to less than or equal to 4 mol %, from greater than or equal to 2 mol % to less than or equal to 3 mol %, or any and all sub-ranges formed from these endpoints. In embodiments, the glass-based substrates may be substantially free or free of B₂O₃.

The glass-based substrate may additionally include Na₂O. In some embodiments, the glass-based substrate may include Na₂O in an amount of from greater than or equal to 0 mol % to less than or equal to 1 mol %. In embodiments, the glass-based substrate may be substantially free or free of Na₂O.

The glass-based substrate may additionally include MgO. In some embodiments, the glass-based substrates may include MgO in an amount from greater than or equal to 0 mol % to less than or equal to 7 mol %, such as from greater than or equal to 1 mol % to less than or equal to 6 mol %, from greater than or equal to 2 mol % to less than or equal to 5 mol %, from greater than or equal to 3 mol % to less than or equal to 4 mol %, or any and all sub-ranges formed from these endpoints. In embodiments, the glass-based substrates may be substantially free or free of MgO.

The glass-based substrate may additionally include CaO, SrO, and/or BaO. In embodiments, the glass-based substrates may be substantially free or free of CaO. In embodiments, the glass-based substrates may be substantially free or free of SrO. In some embodiments, the glass-based substrate is substantially free of free of BaO.

The glass-based substrates may have a Young's modulus that is greater than or equal to 59 GPa. The high Young's modulus of the glass-based substrates increases the efficiency of the conversion of strain to stress, such that the strain generated by water vapor treatment produces a higher compressive stress in glass-based articles formed from the glass-based substrates. In embodiments, the glass-based substrates have a Young's modulus that is greater than or equal to 60 GPa, such as greater than or equal to 61 GPa, greater than or equal to 62 GPa, greater than or equal to 63 GPa, greater than or equal to 64 GPa, greater than or equal to 65 GPa, or more. In some embodiments, the glass-based substrates may have a Young's modulus in the range from greater than or equal to 59 GPa to less than or equal to 66 GPa, such as from greater than or equal to 60 GPa to less than or equal to 65 GPa, from greater than or equal to 61 GPa to less than or equal to 64 GPa, from greater than or equal to 62 GPa to less than or equal to 63 GPa, or any and all sub-ranges formed from these endpoints.

The glass-based substrates may additionally include a fining agent. In some embodiments, the fining agent may include tin. In embodiments, the glass-based substrate may include SnO₂ in an amount from greater than or equal to 0 mol % to less than or equal to 0.5 mol %, such as from greater than 0 mol % to less than or equal to 0.1 mol %. In embodiments, the glass-based substrate may be substantially free or free of SnO₂.

The glass-based substrate may have any appropriate geometry. In some embodiments, the glass-based substrate may have a thickness of less than or equal to 2 mm, such as less than or equal to 1.9 mm, less than or equal to 1.8 mm, less than or equal to 1.7 mm, less than or equal to 1.6 mm, less than or equal to 1.5 mm, less than or equal to 1.4 mm, less than or equal to 1.3 mm, less than or equal to 1.2 mm, less than or equal to 1.1 mm, less than or equal to 1 mm, less than or equal to 900 μm, less than or equal to 800 μm, less than or equal to 700 μm, less than or equal to 600 μm, less than or equal to 500 μm, less than or equal to 400 μm, less than or equal to 300 μm, or less. In embodiments, the glass-based substrate may have a thickness from greater than or equal to 300 μm to less than or equal to 2 mm, such as from greater than or equal to 400 μm to less than or equal to 1.9 mm, from greater than or equal to 500 μm to less than or equal to 1.8 mm, from greater than or equal to 600 μm to less than or equal to 1.7 mm, from greater than or equal to 700 μm to less than or equal to 1.6 mm, from greater than or equal to 800 μm to less than or equal to 1.5 mm, from greater than or equal to 900 μm to less than or equal to 1.4 mm, from greater than or equal to 1 mm to less than or equal to 1.3 mm, from greater than or equal to 1.1 mm to less than or equal to 1.2 mm, or any and all sub-ranges formed from these endpoints. In some embodiments, the glass-based substrate may have a plate or sheet shape. In some other embodiments, the glass-based substrates may have a 2.5D or 3D shape. As utilized herein, a “2.5D shape” refers to a sheet shaped article with at least one major surface being at least partially nonplanar, and a second major surface being substantially planar. As utilized herein, a “3D shape” refers to an article with first and second opposing major surfaces that are at least partially nonplanar. The glass-based articles may have dimensions and shapes substantially similar or the same as the glass-based substrates from which they are formed.

The glass-based articles may be produced from the glass-based substrate by exposure to water vapor under any appropriate conditions. The exposure may be carried out in any appropriate device, such as a furnace with relative humidity control. The exposure may also be carried out at an elevated pressure, such as a furnace or autoclave with relative humidity and pressure control.

In some embodiments, the glass-based articles may be produced by exposing a glass-based substrate to an environment with a pressure greater than or equal to ambient pressure and containing water vapor. The environment may have a pressure greater than or equal to 0.1 MPa, a water partial pressure of greater than or equal to 0.075 MPa, and a temperature greater than 100° C. The use of an elevated pressure allows in the exposure environment allows for a higher concentration of water vapor in the environment, especially as temperatures are increased. As the temperature increases the amount of water available for diffusion into the glass-based substrates to form glass-based articles decreases for a fixed volume, such as the interior of a furnace or autoclave. Thus, while increasing the temperature of the water vapor treatment environment may increase the rate of diffusion of hydrogen species into the glass-based substrate, reduced total water vapor concentration and stress relaxation at higher temperatures produce decreased compressive stress when pressure is constant. As temperatures increase, such as those above the atmospheric pressure saturation condition, applying increased pressure to reach the saturation condition increases the concentration of water vapor in the environment significantly.

At atmospheric pressure (0.1 MPa), the water vapor saturation condition is 99.61° C. As the temperature increases the amount of water available for diffusion into the glass-based substrates to form glass-based articles decreases for a fixed volume, such as the interior of a furnace or autoclave. Thus, while increasing the temperature of the water vapor treatment environment may increase the rate of diffusion of hydrogen species into the glass-based substrate, reduced total water vapor concentration may reduce the effectiveness of the treatment.

As temperatures increase, such as those above the atmospheric pressure saturation condition, applying increased pressure to reach the saturation condition increases the concentration of water vapor in the environment significantly. The saturation condition for water vapor as a function of pressure and temperature is shown in FIG. 3. As shown in FIG. 3, the regions above the curve will result in condensation of water vapor into liquid which is undesirable. Thus, the water vapor treatment conditions utilized herein may preferably fall on or under the curve in FIG. 3, with further preferred conditions being on or just under the curve to maximize water vapor content. For these reasons, the water vapor treatment of the glass-based substrates may be carried out at elevated pressure.

In some embodiments, the glass-based substrates may be exposed to an environment at a pressure greater than or equal to 0.1 MPa, such as greater than or equal to 0.2 MPa, greater than or equal to 0.3 MPa, greater than or equal to 0.4 MPa, greater than or equal to 0.5 MPa, greater than or equal to 0.6 MPa, greater than or equal to 0.7 MPa, greater than or equal to 0.8 MPa, greater than or equal to 0.9 MPa, greater than or equal to 1.0 MPa, greater than or equal to 1.1 MPa, greater than or equal to 1.2 MPa, greater than or equal to 1.3 MPa, greater than or equal to 1.4 MPa, greater than or equal to 1.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 1.7 MPa, greater than or equal to 1.8 MPa, greater than or equal to 1.9 MPa, greater than or equal to 2.0 MPa, greater than or equal to 2.1 MPa, greater than or equal to 2.2 MPa, greater than or equal to 2.3 MPa, greater than or equal to 2.4 MPa, greater than or equal to 2.5 MPa, greater than or equal to 2.6 MPa, greater than or equal to 2.7 MPa, greater than or equal to 2.8 MPa, greater than or equal to 2.9 MPa, greater than or equal to 3.0 MPa, greater than or equal to 3.1 MPa, greater than or equal to 3.2 MPa, greater than or equal to 3.3 MPa, greater than or equal to 3.4 MPa, greater than or equal to 3.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 3.7 MPa, greater than or equal to 3.8 MPa, greater than or equal to 3.9 MPa, greater than or equal to 4.0 MPa, greater than or equal to 4.1 MPa, greater than or equal to 4.2 MPa, greater than or equal to 4.3 MPa, greater than or equal to 4.4 MPa, greater than or equal to 4.5 MPa, greater than or equal to 4.6 MPa, greater than or equal to 4.7 MPa, greater than or equal to 4.8 MPa, greater than or equal to 4.9 MPa, greater than or equal to 5.0 MPa, greater than or equal to 5.1 MPa, greater than or equal to 5.2 MPa, greater than or equal to 5.3 MPa, greater than or equal to 5.4 MPa, greater than or equal to 5.5 MPa, greater than or equal to 5.6 MPa, greater than or equal to 5.7 MPa, greater than or equal to 5.8 MPa, greater than or equal to 5.9 MPa, greater than or equal to 6.0 MPa, or more. In embodiments, the glass-based substrates may be exposed to an environment at a pressure of from greater than or equal to 0.1 MPa to less than or equal to 25 MPa, such as from greater than or equal to 0.2 MPa to less than or equal to 24 MPa, from greater than or equal to 0.3 MPa to less than or equal to 23 MPa, from greater than or equal to 0.4 MPa to less than or equal to 22 MPa, from greater than or equal to 0.5 MPa to less than or equal to 21 MPa, from greater than or equal to 0.6 MPa to less than or equal to 20 MPa, from greater than or equal to 0.7 MPa to less than or equal to 19 MPa, from greater than or equal to 0.8 MPa to less than or equal to 18 MPa, from greater than or equal to 0.9 MPa to less than or equal to 17 MPa, from greater than or equal to 1.0 MPa to less than or equal to 16 MPa, from greater than or equal to 1.1 MPa to less than or equal to 15 MPa, from greater than or equal to 1.2 MPa to less than or equal to 14 MPa, from greater than or equal to 1.3 MPa to less than or equal to 13 MPa, from greater than or equal to 1.4 MPa to less than or equal to 12 MPa, from greater than or equal to 1.5 MPa to less than or equal to 11 MPa, from greater than or equal to 1.6 MPa to less than or equal to 10 MPa, from greater than or equal to 1.7 MPa to less than or equal to 9 MPa, from greater than or equal to 1.8 MPa to less than or equal to 8 MPa, from greater than or equal to 1.9 MPa to less than or equal to 7 MPa, from greater than or equal to 1.9 MPa to less than or equal to 6.9 MPa, from greater than or equal to 2.0 MPa to less than or equal to 6.8 MPa, from greater than or equal to 2.1 MPa to less than or equal to 6.7 MPa, from greater than or equal to 2.2 MPa to less than or equal to 6.6 MPa, from greater than or equal to 2.3 MPa to less than or equal to 6.5 MPa, from greater than or equal to 2.4 MPa to less than or equal to 6.4 MPa, from greater than or equal to 2.5 MPa to less than or equal to 6.3 MPa, from greater than or equal to 2.6 MPa to less than or equal to 6.2 MPa, from greater than or equal to 2.7 MPa to less than or equal to 6.1 MPa, from greater than or equal to 2.8 MPa to less than or equal to 6.0 MPa, from greater than or equal to 2.9 MPa to less than or equal to 5.9 MPa, from greater than or equal to 3.0 MPa to less than or equal to 5.8 MPa, from greater than or equal to 3.1 MPa to less than or equal to 5.7 MPa, from greater than or equal to 3.2 MPa to less than or equal to 5.6 MPa, from greater than or equal to 3.3 MPa to less than or equal to 5.5 MPa, from greater than or equal to 3.4 MPa to less than or equal to 5.4 MPa, from greater than or equal to 3.5 MPa to less than or equal to 5.3 MPa, from greater than or equal to 3.6 MPa to less than or equal to 5.2 MPa, from greater than or equal to 3.7 MPa to less than or equal to 5.1 MPa, from greater than or equal to 3.8 MPa to less than or equal to 5.0 MPa, from greater than or equal to 3.9 MPa to less than or equal to 4.9 MPa, from greater than or equal to 4.0 MPa to less than or equal to 4.8 MPa, from greater than or equal to 4.1 MPa to less than or equal to 4.7 MPa, from greater than or equal to 4.2 MPa to less than or equal to 4.6 MPa, from greater than or equal to 4.3 MPa to less than or equal to 4.5 MPa, 4.4 MPa, or any and all sub-ranges formed from any of these endpoints.

In some embodiments, the glass-based substrates may be exposed to an environment with a water partial pressure greater than or equal to 0.075 MPa, such as greater than or equal to 0.1 MPa, greater than or equal to 0.2 MPa, greater than or equal to 0.3 MPa, greater than or equal to 0.4 MPa, greater than or equal to 0.5 MPa, greater than or equal to 0.6 MPa, greater than or equal to 0.7 MPa, greater than or equal to 0.8 MPa, greater than or equal to 0.9 MPa, greater than or equal to 1.0 MPa, greater than or equal to 1.1 MPa, greater than or equal to 1.2 MPa, greater than or equal to 1.3 MPa, greater than or equal to 1.4 MPa, greater than or equal to 1.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 1.7 MPa, greater than or equal to 1.8 MPa, greater than or equal to 1.9 MPa, greater than or equal to 2.0 MPa, greater than or equal to 2.1 MPa, greater than or equal to 2.2 MPa, greater than or equal to 2.3 MPa, greater than or equal to 2.4 MPa, greater than or equal to 2.5 MPa, greater than or equal to 2.6 MPa, greater than or equal to 2.7 MPa, greater than or equal to 2.8 MPa, greater than or equal to 2.9 MPa, greater than or equal to 3.0 MPa, greater than or equal to 3.1 MPa, greater than or equal to 3.2 MPa, greater than or equal to 3.3 MPa, greater than or equal to 3.4 MPa, greater than or equal to 3.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 3.7 MPa, greater than or equal to 3.8 MPa, greater than or equal to 3.9 MPa, greater than or equal to 4.0 MPa, greater than or equal to 4.1 MPa, greater than or equal to 4.2 MPa, greater than or equal to 4.3 MPa, greater than or equal to 4.4 MPa, greater than or equal to 4.5 MPa, greater than or equal to 4.6 MPa, greater than or equal to 4.7 MPa, greater than or equal to 4.8 MPa, greater than or equal to 4.9 MPa, greater than or equal to 5.0 MPa, greater than or equal to 5.1 MPa, greater than or equal to 5.2 MPa, greater than or equal to 5.3 MPa, greater than or equal to 5.4 MPa, greater than or equal to 5.5 MPa, greater than or equal to 5.6 MPa, greater than or equal to 5.7 MPa, greater than or equal to 5.8 MPa, greater than or equal to 5.9 MPa, greater than or equal to 6.0 MPa, greater than or equal to 7.0 MPa, greater than or equal to 8.0 MPa, greater than or equal to 9.0 MPa, greater than or equal to 10.0 MPa, greater than or equal to 11.0 MPa, greater than or equal to 12.0 MPa, greater than or equal to 13.0 MPa, greater than or equal to 14.0 MPa, greater than or equal to 15.0 MPa, greater than or equal to 16.0 MPa, greater than or equal to 17.0 MPa, greater than or equal to 18.0 MPa, greater than or equal to 19.0 MPa, greater than or equal to 20.0 MPa, greater than or equal to 21.0 MPa, greater than or equal to 22.0 MPa, or more. In embodiments, the glass-based substrates may be exposed to an environment with a water partial pressure from greater than or equal to 0.075 MPa to less than or equal to 22 MPa, such as from greater than or equal to 0.1 MPa to less than or equal to 21 MPa, from greater than or equal to 0.2 MPa to less than or equal to 20 MPa, from greater than or equal to 0.3 MPa to less than or equal to 19 MPa, from greater than or equal to 0.4 MPa to less than or equal to 18 MPa, from greater than or equal to 0.5 MPa to less than or equal to 17 MPa, from greater than or equal to 0.6 MPa to less than or equal to 16 MPa, from greater than or equal to 0.7 MPa to less than or equal to 15 MPa, from greater than or equal to 0.8 MPa to less than or equal to 14 MPa, from greater than or equal to 0.9 MPa to less than or equal to 13 MPa, from greater than or equal to 1.0 MPa to less than or equal to 12 MPa, from greater than or equal to 1.1 MPa to less than or equal to 11 MPa, from greater than or equal to 1.2 MPa to less than or equal to 10 MPa, from greater than or equal to 1.3 MPa to less than or equal to 9 MPa, from greater than or equal to 1.4 MPa to less than or equal to 8 MPa, from greater than or equal to 1.5 MPa to less than or equal to 7 MPa, from greater than or equal to 1.6 MPa to less than or equal to 6.9 MPa, from greater than or equal to 1.7 MPa to less than or equal to 6.8 MPa, from greater than or equal to 1.8 MPa to less than or equal to 6.7 MPa, from greater than or equal to 1.9 MPa to less than or equal to 6.6 MPa, from greater than or equal to 2.0 MPa to less than or equal to 6.5 MPa, from greater than or equal to 2.1 MPa to less than or equal to 6.4 MPa, from greater than or equal to 2.2 MPa to less than or equal to 6.3 MPa, from greater than or equal to 2.3 MPa to less than or equal to 6.2 MPa, from greater than or equal to 2.4 MPa to less than or equal to 6.1 MPa, from greater than or equal to 2.5 MPa to less than or equal to 6.0 MPa, from greater than or equal to 2.6 MPa to less than or equal to 5.9 MPa, from greater than or equal to 2.7 MPa to less than or equal to 5.8 MPa, from greater than or equal to 2.8 MPa to less than or equal to 5.7 MPa, from greater than or equal to 2.9 MPa to less than or equal to 5.6 MPa, from greater than or equal to 3.0 MPa to less than or equal to 5.5 MPa, from greater than or equal to 3.1 MPa to less than or equal to 5.4 MPa, from greater than or equal to 3.2 MPa to less than or equal to 5.3 MPa, from greater than or equal to 3.3 MPa to less than or equal to 5.2 MPa, from greater than or equal to 3.4 MPa to less than or equal to 5.1 MPa, from greater than or equal to 3.5 MPa to less than or equal to 5.0 MPa, from greater than or equal to 3.6 MPa to less than or equal to 4.9 MPa, from greater than or equal to 3.7 MPa to less than or equal to 4.8 MPa, from greater than or equal to 3.8 MPa to less than or equal to 4.7 MPa, from greater than or equal to 3.9 MPa to less than or equal to 4.6 MPa, from greater than or equal to 4.0 MPa to less than or equal to 4.5 MPa, from greater than or equal to 4.1 MPa to less than or equal to 4.4 MPa, from greater than or equal to 4.2 MPa to less than or equal to 4.3 MPa, or any and all sub-ranges formed from any of these endpoints.

In some embodiments, the glass-based substrates may be exposed to an environment with a relative humidity of greater than or equal to 10%, such as greater than or equal to 25%, greater than or equal to 50%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, greater than or equal to 95%, greater than or equal to 99%, or more. In some embodiments, the glass-based substrate may be exposed to an environment with 100% relative humidity. In some embodiments, the water vapor environment may be a saturated water vapor environment.

In some embodiments, the glass-based substrates may be exposed to an environment at with a temperature of greater than or equal to 100° C., such as greater than or equal to 105° C., greater than or equal to 110° C., greater than or equal to 115° C., greater than or equal to 120° C., greater than or equal to 125° C., greater than or equal to 130° C., greater than or equal to 135° C., greater than or equal to 140° C., greater than or equal to 145° C., greater than or equal to 150° C., greater than or equal to 155° C., greater than or equal to 160° C., greater than or equal to 165° C., greater than or equal to 170° C., greater than or equal to 175° C., greater than or equal to 180° C., greater than or equal to 185° C., greater than or equal to 190° C., greater than or equal to 195° C., greater than or equal to 200° C., greater than or equal to 205° C., greater than or equal to 210° C., greater than or equal to 215° C., greater than or equal to 220° C., greater than or equal to 225° C., greater than or equal to 230° C., greater than or equal to 235° C., greater than or equal to 240° C., greater than or equal to 245° C., greater than or equal to 250° C., greater than or equal to 255° C., greater than or equal to 260° C., greater than or equal to 265° C., greater than or equal to 270° C., greater than or equal to 275° C., greater than or equal to 280° C., greater than or equal to 285° C., greater than or equal to 290° C., greater than or equal to 295° C., greater than or equal to 300° C., or more. In some embodiments, the glass-based substrates may be exposed to an environment with a temperature from greater than or equal to 100° C. to less than or equal to 400° C., such as from greater than or equal to 105° C. to less than or equal to 390° C., from greater than or equal to 110° C. to less than or equal to 380° C., from greater than or equal to 115° C. to less than or equal to 370° C., from greater than or equal to 120° C. to less than or equal to 360° C., from greater than or equal to 125° C. to less than or equal to 350° C., from greater than or equal to 130° C. to less than or equal to 340° C., from greater than or equal to 135° C. to less than or equal to 330° C., from greater than or equal to 140° C. to less than or equal to 320° C., from greater than or equal to 145° C. to less than or equal to 310° C., from greater than or equal to 150° C. to less than or equal to 300° C., from greater than or equal to 155° C. to less than or equal to 295° C., from greater than or equal to 160° C. to less than or equal to 290° C., from greater than or equal to 165° C. to less than or equal to 285° C., from greater than or equal to 170° C. to less than or equal to 280° C., from greater than or equal to 175° C. to less than or equal to 275° C., from greater than or equal to 180° C. to less than or equal to 270° C., from greater than or equal to 185° C. to less than or equal to 265° C., from greater than or equal to 190° C. to less than or equal to 260° C., from greater than or equal to 195° C. to less than or equal to 255° C., from greater than or equal to 200° C. to less than or equal to 250° C., from greater than or equal to 205° C. to less than or equal to 245° C., from greater than or equal to 210° C. to less than or equal to 240° C., from greater than or equal to 215° C. to less than or equal to 235° C., from greater than or equal to 220° C. to less than or equal to 230° C., 225° C., or any and all sub-ranges formed from any of these endpoints.

In some embodiments, the glass-based substrate may be exposed to the water vapor containing environment for a time period sufficient to produce the desired degree of hydrogen-containing species diffusion and the desired compressive stress layer. In some embodiments, the glass-based substrate may be exposed to the water vapor containing environment for greater than or equal to 2 hours, such as greater than or equal to 4 hours, greater than or equal to 6 hours, greater than or equal to 8 hours, greater than or equal to 10 hours, greater than or equal to 12 hours, greater than or equal to 14 hours, greater than or equal to 16 hours, greater than or equal to 18 hours, greater than or equal to 20 hours, greater than or equal to 22 hours, greater than or equal to 24 hours, greater than or equal to 30 hours, greater than or equal to 36 hours, greater than or equal to 42 hours, greater than or equal to 48 hours, greater than or equal to 54 hours, greater than or equal to 60 hours, greater than or equal to 66 hours, greater than or equal to 72 hours, greater than or equal to 78 hours, greater than or equal to 84 hours, greater than or equal to 90 hours, greater than or equal to 96 hours, greater than or equal to 102 hours, greater than or equal to 108 hours, greater than or equal to 114 hours, greater than or equal to 120 hours, greater than or equal to 126 hours, greater than or equal to 132 hours, greater than or equal to 138 hours, greater than or equal to 144 hours, greater than or equal to 150 hours, greater than or equal to 156 hours, greater than or equal to 162 hours, greater than or equal to 168 hours, greater than or equal to 200 hours, greater than or equal to 225 hours, greater than or equal to 250 hours, greater than or equal to 275 hours, greater than or equal to 300 hours, or more. In some embodiments, the glass-based substrate may be exposed to the water vapor containing environment for a time period from greater than or equal to 2 hours to less than or equal to 10 days, such as from greater than or equal to 4 hours to less than or equal to 9 days, from greater than or equal to 6 hours to less than or equal to 8 days, from greater than or equal to 8 hours to less than or equal to 168 hours, from greater than or equal to 10 hours to less than or equal to 162 hours, from greater than or equal to 12 hours to less than or equal to 156 hours, from greater than or equal to 14 hours to less than or equal to 150 hours, from greater than or equal to 16 hours to less than or equal to 144 hours, from greater than or equal to 18 hours to less than or equal to 138 hours, from greater than or equal to 20 hours to less than or equal to 132 hours, from greater than or equal to 22 hours to less than or equal to 126 hours, from greater than or equal to 24 hours to less than or equal to 120 hours, from greater than or equal to 30 hours to less than or equal to 114 hours, from greater than or equal to 36 hours to less than or equal to 108 hours, from greater than or equal to 42 hours to less than or equal to 102 hours, from greater than or equal to 48 hours to less than or equal to 96 hours, from greater than or equal to 54 hours to less than or equal to 90 hours, from greater than or equal to 60 hours to less than or equal to 84 hours, from greater than or equal to 66 hours to less than or equal to 78 hours, 72 hours, or any and all sub-ranges formed from any of these endpoints.

In some embodiments, the glass-based substrates may be exposed to multiple water vapor containing environments. In embodiments, the glass-based substrate may be exposed to a first environment to form a first glass-based article with a first compressive stress layer extending from a surface of the first glass-based article to a first depth of compression, and the first glass-based article may then be exposed to a second environment to form a second glass-based article with a second compressive stress layer extending from a surface of the second glass-based article to a second depth of compression. The first environment has a first water partial pressure and a first temperature, and the glass-based substrate is exposed to the first environment for a first time period. The second environment has a second water partial pressure and a second temperature, and the first glass-based article is exposed to the second environment for a second time period. The second environment may be a saturated water vapor environment.

The first water partial pressure and the second water partial pressure may be any appropriate partial pressure, such as greater than or equal to 0.075 MPa. The first and second partial pressure may be any of the values disclosed herein with respect to the water partial pressures employed in the elevated pressure method. In embodiments, the first and second environments may have, independently, a relative humidity of greater than or equal to 10%, such as greater than or equal to 25%, greater than or equal to 50%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 90%, greater than or equal to 95%, or equal to 100%. In some embodiments, at least one of the first environment and the second environment has a relative humidity of 100%.

The first compressive stress layer includes a first maximum compressive stress, and the second compressive stress layer includes a second maximum compressive stress. In embodiments, the first maximum compressive stress is less than the second maximum compressive stress. The second maximum compressive stress may be compared to a compressive stress “spike” of the type formed through multi-step or mixed bath ion exchange techniques. The first and second maximum compressive stress may have any of the values disclosed herein with respect to the compressive stress of the glass-based article. In embodiments, the second maximum compressive stress may be greater than or equal to 50 MPa.

The first depth of compression may be less than or equal to the second depth of compression. In some embodiments, the first depth of compression is less than the second depth of compression. The first depth of compression and the second depth of compression may have any of the values disclosed herein with respect to the depth of compression. In embodiments, the second depth of compression is greater than 5 μm.

The first temperature may be greater than or equal to the second temperature. In embodiments, the first temperature is greater than the second temperature. The first and second temperatures may be any of the temperatures disclosed in connection with the elevated pressure method.

The first time period may be less than or equal to the second time period. In embodiments, the first time period is less than the second time period. The first and second time periods may be any of the time periods disclosed in connection with the elevated pressure method.

In embodiments, any or all of the multiple exposures to a water vapor containing environment may be performed at an elevated pressure. For example, at least one of the first environment and the second environment may have a pressure greater than 0.1 MPa. The first and second environments may have any pressure disclose in connection with the elevated pressure method.

In some embodiments, the multiple water vapor environment exposure technique may include more than two exposure environments. In embodiments, the second glass-based article may be exposed to a third environment to form a third glass-based article. The third environment has a third water partial pressure and a third temperature, and the second glass-based article is exposed to the third environment for a third time period. The third glass-based article includes a third compressive stress layer extending from a surface of the article to a third depth of compression and having a third maximum compressive stress. The third water partial pressure may be greater than or equal to 0.075 MPa. The values of any of the properties of the third environment and third glass-based article may be selected from those disclosed for the corresponding properties in connection with the elevated pressure method.

In some embodiments, the first glass-based article may be cooled to ambient temperature or otherwise removed from the first environment after the conclusion of the first time period and prior to being exposed to the second environment. In some embodiments, the first glass-based article may remain in the first environment after the conclusion of the first time period, and the first environment conditions may be changed to the second environment conditions without cooling to ambient temperature or removing the first glass-based article from the water vapor containing environment.

The methods of producing the glass-based articles disclosed herein may be free of an ion exchange treatment with an alkali ion source. In embodiments, the glass-based articles are produced by methods that do not include an ion exchange with an alkali ion source. Stated differently, in some embodiments the glass-based substrates and glass-based articles are not subjected to an ion exchange treatment with an alkali ion source.

The exposure conditions may be modified to reduce the time necessary to produce the desired amount of hydrogen-containing species diffusion into the glass-based substrate. For example, the temperature and/or relative humidity may be increased to reduce the time required to achieve the desired degree of hydrogen-containing species diffusion and depth of layer into the glass-based substrate.

The methods and glass-based substrate compositions disclosed herein may produce glass-based articles that have a substantially haze-free or haze-free appearance.

Exemplary Embodiments

Low phosphorous glass compositions that are particularly suited for formation of the glass-based articles described herein were formed into glass-based substrates, and the glass compositions are provided in Table I below. The density of the glass compositions was determined using the buoyancy method of ASTM C693-93 (2013). The strain point and anneal point were determined using the beam bending viscosity method of ASTM C598-93 (2013). The Young's modulus was measured by a resonant ultrasonic spectroscopy technique of the general type set forth in ASTM E2001-13, titled “Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts.” The stress optical coefficient (SOC) was measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient.” The refractive index was measured at a wavelength of 589.3 nm. The liquidus temperature was measured in accordance with ASTM C829-81 (2015), titled “Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method.” The liquidus viscosity was determined by measuring the viscosity of the glass at the liquidus temperature in accordance with ASTM C965-96 (2012), titled “Standard Practice for Measuring Viscosity of Glass Above the Softening Point.”

TABLE I Composition A B C D E F G SiO₂ 65.58 67.18 65.53 67.14 63.07 64.86 62.34 Al₂O₃ 11.57 11.60 11.56 11.52 11.64 11.50 11.67 P₂O₅ 2.46 0.97 2.44 0.97 2.40 0.95 2.39 B₂O₃ 1.96 1.91 0.00 0.00 2.75 2.78 3.69 Na₂O 0.10 0.09 0.10 0.09 0.10 0.09 0.10 K₂O 15.79 15.71 15.81 15.77 15.48 15.29 15.23 MgO 0.02 0.02 2.26 2.25 2.27 2.24 2.30 ZnO 2.45 2.47 2.24 2.20 2.23 2.23 2.23 SnO₂ 0.06 0.05 0.06 0.05 0.06 0.05 0.06 Properties Density 2.435 2.442 2.440 2.444 2.434 2.437 2.435 (g/cm³) Strain Pt. 619.2 630.4 699.2 702.2 635.6 623.6 618.2 (° C.) Anneal Pt. 676.9 688.6 761.2 763.4 697.4 682.6 678.5 (° C.) SOC 3.187 3.162 3.066 3.087 3.201 3.223 3.200 (nm/mm/MPa) Refractive 1.4961 1.4984 1.4961 1.4983 1.4971 1.4988 1.4975 Index at 589.3 nm Young's 59.92 61.85 60.81 62.54 59.98 61.50 59.43 Modulus (GPa) 200 P 1744 1807 1724 Temperature (° C.) 35 kP 1281 1315 1264 Temperature (° C.) 200 kP 1175 1222 1159 Temperature (° C.) Liquidus >1345 >1325 1360 Temperature (° C.) Liquidus <13.9 <29.5 9 Viscosity (kP) Composition H I J K L M N O SiO₂ 64.15 64.53 64.82 64.78 63.06 63.15 63.25 64.55 Al₂O₃ 11.57 11.55 11.46 11.50 11.49 11.46 11.44 11.55 P₂O₅ 0.94 0.96 0.48 0.24 0.94 0.47 0.23 0.96 B₂O₃ 3.54 0.00 0.00 0.00 0.00 0.00 0.00 1.86 Na₂O 0.10 0.17 0.22 0.14 0.16 0.16 0.16 0.15 K₂O 15.13 15.80 15.60 15.64 17.43 17.39 17.30 15.49 MgO 2.26 4.79 5.24 5.51 4.77 5.21 5.46 3.26 ZnO 2.24 2.14 2.13 2.13 2.10 2.12 2.10 2.13 SnO₂ 0.06 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Properties Density 2.434 2.459 2.462 2.466 2.467 2.473 2.473 2.445 (g/cm³) Strain Pt. 612.1 703.6 706.9 712.4 695.2 698.9 706.2 643.2 (° C.) Anneal Pt. 670.2 761.4 766.0 770.0 751.7 757.4 763.9 703.6 (° C.) SOC 3.279 3.018 3.008 3.001 2.960 2.952 2.935 3.154 (nm/mm/MPa) Refractive 1.4976 1.5020 1.5032 1.5048 1.5035 1.5049 1.5058 1.5004 Index at 589.3 nm Young's 61.09 64.19 65.03 65.64 63.02 63.98 64.47 62.26 Modulus (GPa) 200 P 1777 1786 1743 1734 1734 Temperature (° C.) 35 kP 1292 1340 1307 1313 1313 Temperature (° C.) 200 kP 1198 1256 1215 1221 1223 Temperature (° C.) Liquidus >1355 >1315 >1315 >1320 >1325 >1300 >1290 >1315 Temperature (° C.) Liquidus <13.1 <56.7 <25.7 <43.6 <53.2 Viscosity (kP) Composition P Q R S T U V W SiO₂ 62.83 63.88 62.52 63.00 61.90 63.05 63.22 64.42 Al₂O₃ 11.57 11.62 11.45 11.73 11.59 10.17 8.48 6.79 P₂O₅ 0.95 0.93 0.94 0.93 0.93 0.25 0.24 0.22 B₂O₃ 1.79 2.69 2.65 3.51 3.28 0.00 0.00 0.00 Na₂O 0.17 0.14 0.16 0.15 0.17 0.00 0.00 0.00 K₂O 17.26 15.29 16.90 15.19 16.68 18.71 20.28 21.10 MgO 3.26 3.28 3.23 3.31 3.27 5.62 5.58 5.38 ZnO 2.13 2.11 2.10 2.13 2.13 2.16 2.15 2.05 SnO₂ 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Properties Density 2.459 2.439 2.453 2.440 2.451 2.480 4.485 2.485 (g/cm³) Strain Pt. 641.5 627.7 619.5 610.2 614.2 677.8 630.1 (° C.) Anneal Pt. 699.9 687.7 676.2 669.5 671.6 733.2 684.3 (° C.) SOC 3.089 3.211 3.140 3.075 3.197 2.897 2.852 2.781 (nm/mm/MPa) Refractive 1.5022 1.5002 1.5019 1.5003 1.5020 Index at 589.3 nm Young's 61.71 61.85 61.43 61.16 60.95 62.74 60.74 58.67 Modulus (GPa) 200 P 1755 1750 1743 1715 1685 Temperature (° C.) 35 kP 1303 1296 1283 1279 1246 Temperature (° C.) 200 kP 1233 1196 1208 1187 1156 Temperature (° C.) Liquidus >1340 >1325 >1340 >1370 >1410 Temperature (° C.) Liquidus <16.5 <22.4 <12.2 <8.5 <3.5 Viscosity (kP) Composition X Y Z SiO₂ 64.55 66.17 67.75 Al₂O₃ 10.04 8.52 6.95 P₂O₅ 0.24 0.23 0.24 B₂O₃ 0.00 0.00 0.00 Na₂O 0.00 0.00 0.00 K₂O 17.43 17.34 17.39 MgO 5.55 5.56 5.50 ZnO 2.14 2.11 2.13 SnO₂ 0.05 0.05 0.05 Properties Density 2.471 2.466 2.461 (g/cm³) Strain Pt. (° C.) Anneal Pt. (° C.) SOC 2.957 2.957 2.938 (nm/mm/MPa) Refractive Index at 589.3 nm Young's 63.22 62.12 61.02 Modulus (GPa) 200 P Temperature (° C.) 35 kP Temperature (° C.) 200 kP Temperature (° C.) Liquidus Temperature (° C.) Liquidus Viscosity (kP)

Samples having the compositions shown in Table I were exposed to water vapor containing environments to form glass articles having compressive stress layers. The sample composition and the environment the samples were exposed to, including the temperature, pressure, and exposure time, are shown in Table II below. The exposure environments were saturated where possible based on the temperature and pressure conditions. For example, the 150° C. at 0.4 MPa and 300° C. 2.6 MPa exposure environments were non-saturation conditions. The resulting maximum compressive stress and depth of compression as measured by surface stress meter (FSM) is also reported in Table II.

TABLE II Example 1 2 3 4 5 6 7 8 Composition A B C D G H I J Treatment 150 150 150 150 150 150 150 150 Temperature (° C.) Treatment 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Pressure (MPa) Treatment 169 169 169 169 169 169 169 169 Time (h) Compressive 401 452 419 443 344 378 448 439 Stress (MPa) Depth of 14 11 15 11 10 9 9 8 Compression (μm) Example 9 10 11 12 13 14 15 16 Composition K L M N O P Q R Treatment 150 150 150 150 150 150 150 150 Temperature (° C.) Treatment 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Pressure (MPa) Treatment 169 169 169 169 169 169 169 169 Time (h) Compressive 438 476 480 498 433 432 400 408 Stress (MPa) Depth of 8 9 8 8 9 7 8 8 Compression (μm) Example 17 18 19 20 21 22 23 24 Composition S T A A A B B B Treatment 150 150 175 175 175 175 175 175 Temperature (° C.) Treatment 0.4 0.4 1 1 1 1 1 1 Pressure (MPa) Treatment 169 169 16 32 72 16 32 72 Time (h) Compressive 368 412 383 361 356 408 372 370 Stress (MPa) Depth of 7 8 10 14 19 7 10 14 Compression (μm) Example 25 26 27 28 29 30 31 32 Composition C C C D D D E E Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 1 1 1 1 1 1 1 1 Pressure (MPa) Treatment 16 32 72 16 32 72 9 16 Time (h) Compressive 381 382 363 394 401 387 319 362 Stress (MPa) Depth of 11 14 20 8 11 17 8 8 Compression (μm) Example 33 34 35 36 37 38 39 40 Composition E F F G G G H H Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 1 1 1 1 1 1 1 1 Pressure (MPa) Treatment 32 16 32 9 16 32 16 32 Time (h) Compressive 326 314 345 291 329 313 340 350 Stress (MPa) Depth of 11 7 9 8 9 11 7 8 Compression (μm) Example 41 42 43 44 45 46 47 48 Composition I I J K K L M M Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 1 1 1 1 1 1 1 1 Pressure (MPa) Treatment 16 32 16 16 32 16 16 32 Time (h) Compressive 380 383 362 420 376 489 473 413 Stress (MPa) Depth of 7 11 6 6 9 7 6 9 Compression (μm) Example 49 50 51 52 53 54 55 56 Composition M N N O O O P P Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 1 1 1 1 1 1 1 1 Pressure (MPa) Treatment 72 16 32 16 32 72 16 32 Time (h) Compressive 420 370 409 364 335 357 366 376 Stress (MPa) Depth of 12 6 9 7 10 13 6 9 Compression (μm) Example 57 58 59 60 61 62 63 64 Composition P Q Q Q R R R S Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 1 1 1 1 1 1 1 1 Pressure (MPa) Treatment 72 16 32 72 16 32 72 16 Time (h) Compressive 365 242 333 337 345 349 378 334 Stress (MPa) Depth of 11 6 9 11 6 10 12 6 Compression (μm) Example 65 66 67 68 69 70 71 72 Composition S T T A A A B B Treatment 175 175 175 200 200 200 200 200 Temperature (° C.) Treatment 1 1 1 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 32 16 32 4 9 16 4 9 Time (h) Compressive 311 322 345 382 375 357 401 371 Stress (MPa) Depth of 9 6 10 10 12 15 8 9 Compression (μm) Example 73 74 75 76 77 78 79 80 Composition B B C C C D D D Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 16 32 4 9 16 4 9 16 Time (h) Compressive 389 373 383 386 359 414 428 384 Stress (MPa) Depth of 12 15 11 13 17 8 10 13 Compression (μm) Example 81 82 83 84 85 86 87 88 Composition E E E E F F F F Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 4 9 16 32 4 9 16 32 Time (h) Compressive 301 313 325 343 341 386 343 348 Stress (MPa) Depth of 8 11 13 16 7 8 10 13 Compression (μm) Example 89 90 91 92 93 94 95 96 Composition G G G G H H H H Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 4 9 16 32 4 9 16 32 Time (h) Compressive 320 309 342 320 299 375 338 351 Stress (MPa) Depth of 8 10 12 16 7 8 9 13 Compression (μm) Example 97 98 99 100 101 102 103 104 Composition I I I J J J J K Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 4 9 16 4 9 16 32 4 Time (h) Compressive 412 449 401 413 368 387 401 443 Stress (MPa) Depth of 7 8 11 6 8 11 13 6 Compression (μm) Example 105 106 107 108 109 110 111 112 Composition K K K L L L M M Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 9 16 32 4 9 16 4 9 Time (h) Compressive 389 395 396 422 431 414 467 456 Stress (MPa) Depth of 8 10 12 6 8 11 6 8 Compression (μm) Example 113 114 115 116 117 118 119 120 Composition M N N N O O O P Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 16 4 9 16 4 9 16 4 Time (h) Compressive 411 357 443 411 329 370 353 347 Stress (MPa) Depth of 10 6 8 10 6 9 11 6 Compression (μm) Example 121 122 123 124 125 126 127 128 Composition P P Q Q Q R R R Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 9 16 4 9 16 4 9 16 Time (h) Compressive 411 373 392 351 346 368 371 338 Stress (MPa) Depth of 8 10 6 7 10 6 9 10 Compression (μm) Example 129 130 131 132 133 134 135 136 Composition S S S T T T A B Treatment 200 200 200 200 200 200 225 225 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 2.6 2.6 Pressure (MPa) Treatment 4 9 16 4 9 16 4 4 Time (h) Compressive 320 385 372 312 417 370 349 377 Stress (MPa) Depth of 6 8 10 6 9 10 14 11 Compression (μm) Example 137 138 139 140 141 142 143 144 Composition C D E F G H I I Treatment 225 225 225 225 225 225 225 225 Temperature (° C.) Treatment 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 4 4 4 4 4 4 4 9 Time (h) Compressive 345 408 322 348 320 349 401 401 Stress (MPa) Depth of 15 12 12 11 12 9 11 13 Compression (μm) Example 145 146 147 148 149 150 151 152 Composition J J K K L M M N Treatment 225 225 225 225 225 225 225 225 Temperature (° C.) Treatment 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 4 9 4 9 9 4 9 4 Time (h) Compressive 390 390 384 402 408 428 430 429 Stress (MPa) Depth of 10 11 9 11 13 10 11 9 Compression (μm) Example 153 154 155 156 157 158 159 160 Composition N O O P P Q Q R Treatment 225 225 225 225 225 225 225 225 Temperature (° C.) Treatment 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 9 4 9 4 9 4 9 4 Time (h) Compressive 433 351 361 354 417 391 387 375 Stress (MPa) Depth of 11 10 12 9 10 9 10 10 Compression (μm) Example 161 162 163 164 165 166 167 168 Composition R S S T T A B C Treatment 225 225 225 225 225 250 250 250 Temperature (° C.) Treatment 2.6 2.6 2.6 2.6 2.6 4 4 4 Pressure (MPa) Treatment 9 4 9 4 9 4 4 4 Time (h) Compressive 341 399 394 368 374 307 332 327 Stress (MPa) Depth of 11 9 11 10 11 20 15 21 Compression (μm) Example 169 170 171 172 173 174 175 176 Composition D D E E F F G G Treatment 250 250 250 250 250 250 250 250 Temperature (° C.) Treatment 4 4 4 4 4 4 4 4 Pressure (MPa) Treatment 4 9 4 9 4 9 4 9 Time (h) Compressive 351 314 303 288 319 298 298 287 Stress (MPa) Depth of 12 23 17 22 14 19 16 21 Compression (μm) Example 177 178 179 180 181 182 183 184 Composition H H E F G H K M Treatment 250 250 275 275 275 275 300 300 Temperature (° C.) Treatment 4 4 6 6 6 6 2.6 2.6 Pressure (MPa) Treatment 4 9 4 4 4 4 96 96 Time (h) Compressive 309 296 256 263 254 253 199 161 Stress (MPa) Depth of 13 17 23 19 21 18 66 72 Compression (μm) Example 185 186 187 188 189 190 191 192 Composition N O P A B C U V Treatment 300 300 300 150 150 150 150 150 Temperature (° C.) Treatment 2.6 2.6 2.6 0.5 0.5 0.5 0.5 0.5 Pressure (MPa) Treatment 96 96 96 32 32 32 32 32 Time (h) Compressive 166 129 109 378 377 359 402 531 Stress (MPa) Depth of 98 73 68 9 6 9 5 5 Compression (μm) Example 193 194 195 196 197 198 199 200 Composition X X Y Y Z Z E E Treatment 150 150 150 150 150 150 175 175 Temperature (° C.) Treatment 0.5 0.5 0.5 0.5 0.5 0.5 0.76 0.76 Pressure (MPa) Treatment 16 32 16 32 16 32 16 32 Time (h) Compressive 465 381 479 482 484 457 339 329 Stress (MPa) Depth of 4 5 4 5 4 5 8 10 Compression (μm) Example 201 202 203 204 205 206 207 208 Composition E F F F G G G G Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Pressure (MPa) Treatment 72 16 32 72 6 316 32 72 Time (h) Compressive 355 365 364 380 295 8 311 336 Stress (MPa) Depth of 14 6 8 10 5 13 10 13 Compression (μm) Example 209 210 211 212 213 214 215 216 Composition H H H U U X X Y Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Pressure (MPa) Treatment 16 32 72 16 32 16 32 16 Time (h) Compressive 367 382 382 506 487 525 458 479 Stress (MPa) Depth of 5 8 10 5 6 5 7 5 Compression (μm) Example 217 218 219 220 221 222 223 224 Composition Y Z Z U V X Y Z Treatment 175 175 175 175 175 175 175 175 Temperature (° C.) Treatment 0.76 0.76 0.76 1 1 1 1 1 Pressure (MPa) Treatment 32 16 32 16 16 16 16 16 Time (h) Compressive 461 466 465 458 475 439 440 433 Stress (MPa) Depth of 7 5 6 7 6 7 7 7 Compression (μm) Example 225 226 227 228 229 230 231 232 Composition U U U V X X X Y Treatment 200 200 200 200 200 200 200 200 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pressure (MPa) Treatment 4 9 16 4 4 9 16 4 Time (h) Compressive 499 452 432 508 408 420 430 461 Stress (MPa) Depth of 6 8 9 5 6 8 10 6 Compression (μm) Example 233 234 235 236 237 238 239 240 Composition Y Y Y Y E F G H Treatment 200 200 200 200 225 225 225 225 Temperature (° C.) Treatment 1.6 1.6 1.6 1.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 9 16 4 9 16 16 16 16 Time (h) Compressive 427 410 432 408 313 332 310 322 Stress (MPa) Depth of 8 10 9 8 20 16 18 15 Compression (μm) Example 241 242 243 244 245 246 247 248 Composition A C E F G H O O Treatment 250 250 250 250 250 250 250 250 Temperature (° C.) Treatment 4 4 4 4 4 4 4 4 Pressure (MPa) Treatment 1 1 1 1 1 1 4 16 Time (h) Compressive 361 379 333 357 322 346 346 306 Stress (MPa) Depth of 12 13 11 9 10 8 13 23 Compression (μm) Example 249 250 251 252 253 254 255 256 Composition P P Q Q R R S U Treatment 250 250 250 250 250 250 250 250 Temperature (° C.) Treatment 4 4 4 4 4 4 4 4 Pressure (MPa) Treatment 4 16 4 16 4 16 4 4 Time (h) Compressive 346 297 339 289 336 295 329 290 Stress (MPa) Depth of 12 22 12 20 13 22 12 12 Compression (μm) Example 257 258 259 260 261 262 263 264 Composition X Y A A C C D E Treatment 250 250 300 300 300 300 300 300 Temperature (° C.) Treatment 4 4 2.6 2.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 4 4 24 24 24 24 24 24 Time (h) Compressive 371 253 136 35 177 108 103 175 Stress (MPa) Depth of 13 10 55 113 57 114 94 45 Compression (μm) Example 265 266 267 268 269 270 271 272 Composition G H H Q R S T Y Treatment 300 300 300 300 300 300 300 300 Temperature (° C.) Treatment 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Pressure (MPa) Treatment 24 24 24 96 96 96 24 24 Time (h) Compressive 176 156 72 91 108 88 178 106 Stress (MPa) Depth of 42 38 74 65 67 71 38 39 Compression (μm)

The results in Table II demonstrate that the compressive stress increases and the depth of layer decreases as the P₂O₅ content of the glass compositions is reduced. Additionally, the diffusivity of hydrogen species in the glass is maintained even for low P₂O₅ contents to an extend that allows the formation of compressive stress layers in the glass-based articles on exposure to water vapor containing environments. In comparison, glass compositions that are free of P₂O₅ have not been shown to be capable of producing a compressive stress layer sufficient to measure with a surface stress meter.

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims. 

What is claimed is:
 1. A method, comprising: exposing a glass-based substrate to a steam environment with a pressure greater than or equal to 0.1 MPa, and a temperature of greater than or equal to 150° C. to form a glass-based article with compressive stress layer extending from the surface of the glass-based article to a depth of compression and a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 10 MPa, a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer, and the glass-based substrate comprises: greater than or equal to 55 mol % to less than or equal to 70 mol % SiO₂, greater than or equal to 5 mol % to less than or equal to 13 mol % Al₂O₃, greater than or equal to 0.1 mol % to less than or equal to 3 mol % P₂O₅, greater than or equal to 14 mol % to less than or equal to 23 mol % K₂O, and greater than or equal to 1 mol % to less than or equal to 4 mol % ZnO.
 2. The method of claim 1, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 5 mol % B₂O₃.
 3. The method of claim 1, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 1 mol % Na₂O.
 4. The method of claim 1, wherein the glass-based substrate is substantially free of Na₂O.
 5. The method of claim 1, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 7 mol % MgO.
 6. The method of claim 1, wherein the glass-based substrate comprises greater than or equal to 0 mol % to less than or equal to 0.5 mol % SnO₂.
 7. The method of claim 1, wherein the glass-based substrate comprises a Young's modulus of greater than or equal to 59 MPa.
 8. The method of claim 1, further comprising exposing the glass-based article to a second steam environment with a second pressure and a second temperature, wherein the second steam environment is a saturated steam environment.
 9. The method of claim 1, wherein the glass-based article comprises a thickness of less than or equal to 2 mm.
 10. The method of claim 1, wherein the glass-based article comprises a compressive stress of greater than or equal to 100 MPa.
 11. The method of claim 1, wherein the glass-based article comprises a compressive stress of greater than or equal to 300 MPa.
 12. The method of claim 1, wherein the depth of compression is greater than or equal to 6 μm.
 13. The method of claim 1, wherein the depth of compression is greater than or equal to 10 μm.
 14. The method of claim 1, wherein the glass-based article has a substantially haze-free appearance.
 15. The method of claim 1, wherein the glass-based article is not subjected to an ion-exchange treatment with an alkali ion source.
 16. A method, comprising: exposing a glass-based substrate to a steam environment with a pressure greater than or equal to 0.1 MPa, and a temperature of greater than or equal to 150° C. to form a glass-based article with compressive stress layer extending from the surface of the glass-based article to a depth of compression and a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer, wherein the glass-based article comprises a thickness of less than or equal to 2 mm, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 100 MPa, a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer, and the glass-based substrate comprises: greater than or equal to 55 mol % to less than or equal to 70 mol % SiO₂, greater than or equal to 5 mol % to less than or equal to 13 mol % Al₂O₃, greater than or equal to 0.1 mol % to less than or equal to 3 mol % P₂O₅, greater than or equal to 14 mol % to less than or equal to 23 mol % K₂O, greater than or equal to 1 mol % to less than or equal to 4 mol % ZnO, and greater than or equal to 0 mol % to less than or equal to 5 mol % B₂O₃.
 17. The method of claim 16, wherein the glass-based article has a substantially haze-free appearance.
 18. A method, comprising: exposing a glass-based substrate to a steam environment with a pressure greater than or equal to 0.1 MPa, and a temperature of greater than or equal to 150° C. to form a glass-based article with compressive stress layer extending from the surface of the glass-based article to a depth of compression and a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer, wherein the glass-based article comprises a thickness of less than or equal to 2 mm, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 100 MPa, a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer, and the glass-based substrate comprises: greater than or equal to 55 mol % to less than or equal to 70 mol % SiO₂, greater than or equal to 5 mol % to less than or equal to 13 mol % Al₂O₃, greater than or equal to 0.1 mol % to less than or equal to 3 mol % P₂O₅, greater than or equal to 14 mol % to less than or equal to 23 mol % K₂O, greater than or equal to 1 mol % to less than or equal to 4 mol % ZnO, and greater than or equal to 0 mol % to less than or equal to 7 mol % MgO.
 19. The method of claim 18, wherein the glass-based article has a substantially haze-free appearance.
 20. The method of claim 18, wherein the glass-based article comprises a compressive stress of greater than or equal to 300 MPa. 